Manufacture of glycol pectates and pectinates



I Patented Sept. 19,1950- t I 1 MANUFACTURE OF GLYCOL PECTATES I FAND'PECTINATES' t This invention relates:

' fied in important respects. t

' The constitution 0f the'pectic clearly establishedlb'u t it is known that they are high polymers, usually hal'ving colloidalproperties" It is also established that they contain carboxyl groups which enable them to form both normal and acid salts with bases 3 ln the natural occurrence of these substances, part 0153,11 of the carboxyl groups are esterified by linethyl groups When only partially esterified the substances are known asv pectinic acids whiletheptermpectic acids is applied to those essentially free from s methyle'ster groups; Th

report, adopted at the 1944' Springmeeting of;

. American Chemical Society -(Chemi a1e nd not intended to include food products conta'ining' only small proportions ofsuch ubstancesi II Y We have discovered that by reacting either pectic or pectinic acidwithanalkyleneoxide the calcium reactivity of the acid is reduced while the equivalent weight and the tolerance formidityareincreased. "Each of pheseh ngesisbene-, ficialfin pne'or anotherutiliz'atio" 'ofthe product" ofthe reaction, which tends-e150 to -increase;

water-solubility and'to impart 'that fproperty to if v the normally insoluble pectic acids.

In carrying out this reaction ther'eiiowin'g ge'n-' eral procedure is followed: First (preierably but not necessarily) any base or bases which-may be in combination with. the acid are remoyed by treating, the pectics'ubstanoe with a dilute, acidifiecl, aqueous solution of a water -miscible alcohol, A mixture of 100 parts z-propanol, .61 parts water 4 'chloric acid is i V TiflhiSQW: tureleaves the w rlub e e i nd-pe ic? t e n solid form d-reme e zt cha es trpmi and 815 a parts concentrated by suitable for this purpose. Applicat ,re'a tions betweentheof esterificatiom Th loweralkylene oxides (epoxyparaiflinsfa nd vari ous pectic substances by which 'the p roperties characteristic of the original substance are modi-yi A l i r -takenn r 3ifr po t c mi te bi P i iQn. fr 'ul: tural an'd Food ChemistryQAme can phemicalg p ea t m er:

7' f fllr nold teinei Jolla, and Aaron Miller, M 4 San Diego,"Calif., assignors to. Kelco-Company, "sanpiegotpalifg 'a corporation of Delaware No Drawing. :LApplicsltion June 15, 1946,

, .ria,l'No.677,116 p v pectic substancefis then; thi .o a s m la m ture;

' 1 about 50% solids bygthe additionof water. Wetg with reactivity. This 50% relation Of water'to pectic substance is notc'ritical but in most cases};

is favor-able to complete reaction.

On the incorporation of the alkylene oxide with the dampened pectic substance, reaction occurs spontaneously with the generation of heat. In

' the modification referred to hereinafter as the low pressure metho'd addition of the oxidejis performed at atmospheric pressure and temperature and with constant stirring, the rate of addie tion being so controlled as to maintain the tem-,

"perature slightly belowv14=5 C. in the case of 1,2

the'highpressure?method the-dampened pectic substanb'is 'pl'a'ced inaclosedstirring vessel pro--' vided with a jacket -for heating' or cooling and the temperature is maintained at" a somewhat higher level, sayaabout 50 "0., the oxide being introduced through a pressure feeding device at suc'hrat'e" as to'maintain the vapor pressure in the stirring essel at about "104i gauge. After all the 1 oxide hastbeen added, heating and agitation are continued for at least an hounpafter which the j mass is allowed to stand over night toallow the reaction to come to completion.

The reaction product is usually a powder, or a mass which is-readily friable afterclryin'gfin an air stream at5U/55 C. of a g y consist?" ency, as sometimes occurs, it should be'leached with alcohol and then dried, after which it may readily be ground to a powder; 1

The effects produced by these reactions on v'ari- OllSlIlCfi-C substancesare 'illustratedbyjtheresults ofthafollowingexperiments: v. Experiment rirr'edtm'eniw commercial Mathis ;,'I' hr ee;icommercial:pectins-of the jellying type combination t e ne e n inl de ass (Nos anda th irs-c trus.. ins: a d lie a apple pectin) were treated, without acidification and by the low pressure method, with 1,2 propylene oxide and the properties of each product were compared with those of the original substance:

Pectin #1 Pectin #2 Pectin #3 Orig- Prod- Orig- Prod- Orig- Prodinal uct inal uct inal uct .0 114 0:0 1:?5 0:0] v1:1 Yes Yes Yes Yes I Yes Yes Low 2/700 2/1340 2/620 2/1500 2/1550 2/3. 0 1/6. 4 1/2. 7 1/4 7 1/3.1 1/3. 2 1,300 6 097 1,470 2,990 632 7%}.- High N one Fair Low High Fair A=molecular ratio pectinic substance to alkylene oxide. B=solubility in water.

C-viscosity in aqueous solution, e. 2/,700=.7Q0;cc ntigoises in:

2% solution.

solution.

E =equivalent weight. F=rclative calcium reactivity.

Experiment 2.-Treatment of pectimc acid A commercial apple pectin was treated" acidified dilute alcohol as-above described, liberating the pectinic acid. Theproduct was then treated with different proportions of 1 1,-2- p'ro--- pylene oxide and the properties- 0f -theproducts were compared 'wi-tlrtho'se orn-1e original pec- A': molecular ratio pectinic acid-to alkylene oxide.

B =solubility inwater.

C =visc0sity ingivenaqueoussolution cg -2/. l600=1500 poises in 2% solution.

aqueous solution.

E =equivalent weight. F=relativecalciu1n reactivity. G=.treat1n ent method used, e. g., L. P 1ovz,pressur e. 1 Reacted at 38% solids. All other tests at 50% solids.

Experiment 3.-+Tr'eatment 'ojpectic acid' A sample of commercial pectic acid, substan tially, free frommethox g groups was treated; with various proportions of:,l,2 propylene oxide,- and; e. pr pertie i; he; products;v were, compared.

w th thoseofthe or inal cid A =Inol ecular ratiopectic acid. to alkylene oxide. Bd= solubility in water: (a) incompletely soluble, (b) slightinsoluble res1 ue.

C= viscosity in centipoiSeS in 5%aqueoussolution.

D==pH value in 1% aqueous solution;

Ej equivalent weight.

F=rclative calcium reactivity.

G =treatment method used.

The results of 'theabove experimentsevidence material changes in properties following fromthe, reaction, which may be generalizedkasfol lows:

Pectins (Experiment 1-1) '--'I-he-;princ'ip'al 1 effect D=hydrogen ion concentration, e. g., 2/3:0 '=pH3'-.'0 iir-2%"aqueous centi-- Products" 1:1 111.5. 1:2 1:4 1:5- (a) (b)' Yes Y'es Yes 50: l 135., 105. 120'.

3:91 464" .585 893- 1030 High Fair. Fair. .None Traces.

tins is in lowering the calcium reactivity. The original No. 1 pectin sets to a gel when contacted with calcium salts while the products of the treatments are approximately or entirely nonreactive. In the case of the other two pectins, both the raw material and the product are reactive, but the reactivity of the products is so reduced as to make them milk soluble whereas the original pectins are substantially insoluble in milk.

Pectih'z'c acids (Experiment 2).=The hydroxy- .alkylatio'n ofthe carboxyl' groups of the pectinic acids brings about increased water-solubility, increased solubility in acidic solutions and decreased calciumreactivity. These properties are progressively accentuated as the equivalent weight (degree of esterification) is increased.

' Pectic acid (Experiment 3) .The most important result. of the. application of the reaction to pectic acid is to impart the water-solubility in which this acid'-' is totally lacking. As in the treatment of other classes of pectic substances, the reactivity with alkaline-earth metals is reducedoi' destroyed.

In all cases, esterification of the free carboxyl groups increasesthe equivalent weighta'nd reduces the= proportion of a base with whichthe' product will combine: for reducing the equivalent weight (by'deniethyl oxylat'ion) have been proposed and" used, this is thefirst commerciallyworkable" disclosure, so far as-we are aware, of a method'for increasing the equivalent-"weight, or for increasing the molecu1ar weightother than 'bycombination with a base: a

In the above'experiments the same epo'xyparailin (1,2 propylene oxide) was used'throughout, toavoid the introduc'tion of a variableinto the operation; The reactior'i however; isnotso lim 4O 5 ited but is *a general one,' 'at' least up to the point of lengthening: hydrocarbon chain at which the oxidebecomes substantially water-insoluble and possibly; under more -stren'u'ous reaction conditions; even beyond'this point: This isillustrated *by the results of the following experiments:

Experiment 4.,Reactio'1r-with' ethylene oxide- Pectinio. acid.-. prepared from apple pectinwas dampenedtwithwater. to- 50%. solids-"and reacted by, the;high.pressure method-with. an excessof: ethylene. oxide for seven hours. had, 95%. of .the; free-carboxyl. gro'ups esterified and a 2%-=aqueous@solut1onhad a .pH value of 5.9.

P'ctifii id m atme peach was dampened of-the application ofth'e treatment tothe pee of the free carbojiyl groups ejs terifid and a 2% aqueous solution showeda pI-I'Tv'alue of 5.5.

Pectinic acid prepared from-citruspectinwas the--=carboXyl-'groups neutralized--wi'th ammonium hydroxide; The partially-neutralized product was reactedbythe high pressuremethod" with" two mole'soffljZ epoxybutane fortz ihour's. Theprod uct-"hak1'-67%'=*of the availabie'carboxyl groups 05 l e 'nee a fter partm neutraliza tion-i-esterifiedz While several processes The product'- Experiment 7&4Reaetion withpentylene oxide iPectic a cid' from citrus fruit was, dampened to 50% solids and reacted for 2ghours by;thehigh pressure method with threemoles. 1 ,2 pentylene oxide. The product was 89% es'terified and had a pI-I- i'n2% aqueous solution of5.7. I jdmerime t 8.- Reaction with. hleptylene ozride Pectic acid from a citrus source was dampened to 50 solids and reacted by the high pressure method-with three and one-half molesuof hepi l Pectic acid from a citrus source was dampened with water to 50% solids and reacted for 24 hours with five moles oi octylene oxide by the high pressure method. The product was 32% esterifled. v

The reaction between a pectic substance and 1,2 propylene oxide (as an example of the group of alkylene oxides) may be generalized as follows, R. being any pectic substance:

oriore-onw R-oooH sFcoo-oni-cnone-onr the former being a primary, the latter a secondary alcohol ester. It appears highly probable that the reaction product is a mixture of the two esters.

The product of the reaction may be characterized loosely as a glycol pectate or pectinate;

more accurately as the addition product of an alkyleneoxide and a pectic substance, or as a pectic substance having at least one of its carboxyl hydrogens replaced by an alcohol radical. The definition as a glycol pectate is not strictly accurate if the pectic substance is pectinic rather than 7 At the present time there is not, so far as We are aware, any known, practicable method for bringing about this change, the known reactions to which these substances are subjected being for the purpose of de-esterifying and thereby lowering the equivalent weight. .It is, of course, known to convert these pectic substances to the form of salts, with a relatively small increase'in molecular weight, but this step brings about 'a change in properties whch for many purposes is undesirable.

The above process, producing a wholly organic pectic substance, increases the water-solubility of the parent substance; in the case of pectic acid imparting water-solubility to an initially insoluble substance. It also decreases, to a marked degree, the reactivity of the parent subsubstances in some of their most important applications.

v tylene oxide. Theproduct ,was.7 5 esterified stance with acids and with the alkaline-earth 1 salts, thereby increasing the utility of the pectic -Weclaimasourinvention: V: a 1 v The method of modifying-the propert a substance selected from the group consisting of the pectins, the pectinic acids andpecticacid and having at least one free carboxyl group which consists in esterifying said substance withat least one equivalent of an alkylene oxidecontainingnot more than eight carbon atoms and which is at least slightly soluble in water.

2. The method of modifying the assages;

a substance selected from the group consisting of the' pectins, the pectinic acids and pectic acid and having at least oneiree carboxyl group w hich consists in esterifying said substance with at least one equivalent. of an alkylene oxide containing not more than eight carbon atoms. I

3. The method of modifying the properties ofa substance. seleoted-irom the group consisting of the pectins, the pectinic acids and pectic acid which consists in freeing any neutralized carboxyl groups in said substance and thereafter esteri- .iying the resultant free organic acid with at the pectins, the pectinic acids and pectic acid which consists intreating said substance with a water-diluted acid-alcohol mixture to free a y neutralized carboxyl groups in said substance; expelling the alcohol from the resultant free organic acid, and esterifying said acid with at least one equivalent of an alkylene oxide containing not more than eight carbon atoms in the presence of a quantity of water not materially less than the dry weight of said acid.

5. A hydroxyalkyl ester of a pectic substance selected from the group consisting of the pectins, the pectinic acids and pectic acid: a water-soluble, solid body, characterized by a higher equivalent weight and a lesser reactivity with calcium ions than the parent pectic substance, said ester containing at least one hydroxyalkyl radical having not to exceed eight carbon atoms.

6. A hydroxyalkyl ester of a substance selected from the group consisting of the pectins, the pectinic acids and pectic acid: a water-soluble, solid body, characterized by a higher equivalent weight and a lesser reactivity with calcium ions than the parent substance, said ester containing at least one hydroxyalkyl radical having not to exceed eight carbon atoms.

'7. A hydroxyalkyl ester of a substance selected from the group consisting of the pectins, the pectinic acids and pectic acid: a water-soluble, solid body, substantially nonreactive with calcium ions, said ester containing at least one hydroxyalkyl radical having not to exceed eight carbon atoms.

8. A hydroxyalkyl ester of a substance selected from the group consisting of the pectins, the peetinic acidsand pectic acid and containing carboxyl groups: a water-soluble, solid body in which at least one of said carboxyl groups has its hydrogen replaced by a hydroxyalkyl radical containing not more than eight carbon atoms.

9. A hydroxyalkyl ester of a substance selected from the group consisting of the pectins, the pectinic acids and pectic acid and containing carboxyl' groups: a water-soluble, solid body in which at least one of said carboxyl groups has its hydrogen replaced by a hydroxypropyl radical.

10. A hydroxyalkyl ester of pectic acid: a solid body, at least partially soluble in water, in which at least one of the carboxyl groups of said acid '7 pas it's hydrdgxi repiaed by a hyarcxyamm rad? 6&1tinfiihifig fidtinbi'thn ight carbon atoms. L hyiiriikjfallkyl ester of- 'pectinic acid: a jfir sdhible, solid bodyin which =31. least one 'of t alf'boiiyi grot'ipsof said acid has its hydrogenf izhearboxyl groups of said acidhES-itshydiO- 15 6 gen replaced by ahydioxypropy-l radical.

-'- ARNOhD B. STEINER.

AARON'MILLER.

"REFERENCES cITEIi The' f lljdwing references are of record in. the file of this patient:-

' UNITED'STA-TEQ PATENT Number v Name Date v 2,156,223 Myers Apr. 25 1 939 2,163,621 Myers Ju n 27, 1939 2,189,194.) VGrifiith et a1 Feb 13,. 1940 2,232,926 Peterson Feb 25, ,1 4l

Steiner Aug, 19, 1947 OTHER REFERENCES Hinton: Fruit Pecbins, London 1939, pp. 64 and 

1. THE METHOD OF MODIFYING THE PROPERTIES OF A SUBSTANCE SELECTED FROM THE GROUP CONSISTING OF THE PECTINS, THE PECTINIC ACIDS AND PECTIC ACID AND HAVING AT LEAST ONE FREE CARBOXYL GROUP WHICH CONSISTS IN ESTERIFYING SAID SUBSTANCE WITH AT LEAST ONE EQUIVALENT OF AN ALKYLENE OXIDE CONTAINING NOT MORE THAN EIGHT CARBON ATOMS AND WHICH IS AT LEAST SLIGHTLY SOLUBLE IN WATER. 